Photographic material for the silver dyestuff bleaching process

ABSTRACT

This invention relates to photographic material for the silver dyestuff bleaching process. The material contains new yellow trisazo dyestuffs as image dyestuffs. The trisazo dyestuffs are obtainable by condensing in the molecular ratio 2:1 an aminomonoazodyestuff with an asymmetrically built azo compound containing two carboxylic acid chloride groups.

United States Patent Frohlich et al.

PHOTOGRAPHIC MATERIAL FOR THE SILVER DYESTUFF BLEACHING PROCESSInventors: Alfred Frohlich, Marly; Hansrolf Loeffel, Berne, both ofSwitzerland Assignee: Ciba-Geigy AG, Basel, Switzerland Filed: Sept. 20,1973 Appl. No.: 399,207

Related U.S. Application Data Continuation-inpart of Ser. No. 284,801,Aug. 30, 1972, abandoned, which is a division of Ser. No. 798,792, Feb.12, 1969, abandoned.

Foreign Application Priority Data Feb. 15, 1968 Switzerland ..2253/68U.S. Cl. 96/99; 96/20; 96/73;

260/169 Int. Cl G03c 1/10 Field of Search 96/99, 73

[ Apr. 15, 1975 [56] References Cited UNITED STATES PATENTS 2,286,7146/1942 Chechak 96/99 3,443,953 5/1969 Loeffel 96/99 3,716,368 2/1973Froehlich et a1 96/99 3,749,576 7/1973 Piller 96/99 Primary Examiner J.Travis Brown Attorney, Agent, or Firm.loseph G. Kolodny; Edward McC.Roberts; Prabodh l. Almaula [5 7] ABSTRACT 5 Claims, No DrawingsA-N=N-B-Nl-lCO-E wherein A denotes a benzene or naphthalene residuewhich may be substituted by a halogen atom or an alkyl, alkoxy, nitro oracetylamino group and contains 1 to 3 sulphonic acid groups, B denotes abenzene residue which may be substituted by at most 2 halogen atoms oralkyl, alkoxy. hydroxyalkoxy, alkoxyalkoxy, acylamino, carboxyacylamino(for example a residue of formula HOOCCH -CH CONH), carboxyalkyl,carboxy or phenoxy groups or denotes a naph- 7 thalene residue, andwherein D denotes a benzene or naphthalene residue or a triazoleresidue, E deontes a benzene residue and G denotes a hydrogen atom or analkyl group containing l to 5 carbon atoms, D and E each areunsubstituted or substituted by a halogen atom or an alkyl, alkoxy orphenyl group, the residues D and E -OG being different from one another,OG being bound to E in 2- or 4-position with relation to the azo group,A-N=NBNHCO being bound to D in non-adjacent position with relation tothe azo group and AN= NBNH--C O- being bound to E in 3-position withrelation to the azo group. naphthalene being The residue A of formula lmay be for example derived from the following amines:

2-aminonaphthalene-4,8-disulphonic acid, Z-amino-6-chloronaphthalene-4.8-disulphonic acid, 2-amino-6-acetylaminonaphthalene-4,8-disulphonic acid, 2-amino-6-nitronaphthalene-4,8-disulphonic acid, 2-aminonaphthalene-S,7-disulphonic acid, 1-aminonaphthalene-3,o-disulphonic acid, 2-

aminonaphthalene-4,6,8-trisulphonic acid, 3-amino-4-methoxybenzenesulphonic, sulphonic acid and1-aminobenzene-2,5-disulphonic acid.

The residue B of formula l may for example be derived from the followingamines: aminobenzene. lamino2- or -3-methylbenzene, l-amino-2,5- or-2,6- dimethylbenzene. l-amino-Z-or -3-methoxybenzene,l-amino-Z-ethoxybenzene. l-amino-2-B-hydroxyethoxybenzene,l-amino-Z-B-methoxyethoxy-S- methylbenzene,l-amino-3-acetylaminobenzene, lamino-3-n-butyrylaminobenzene, l-amino-3-SOH l-aminobenzene-2- l-amino-3- l-amino-3-acetylamino-6-l-amino-3-propionylamino-6- l-amino-3-n-butyrylamino-6-l-amin0-3-isobutyrylamino-6- l-amino-Z-acetylamino-S-propionylaminobenzene, isobutyrylaminobenzene, methylbenzene,methylbenzene, methylbenzene, methylbenzene,

methylbenzene, l-amino-2-propionylamino-5- methylbenzene,l-amino-2-propi0nylamino-5- methylbenzene, l-amino-2-n-butyrylamino-S-methylbenzene, l-amino-2-isobutyrylamino-S methylbenzene,l-amino-2-methoxy-5methylbenzene,

l-amino-2-methyl-5-methoxybenzene, l-amino-3- chlorobenzene,I-amino-2-chloro-5-methoxybenzene,

l-amino-2-methoxy-S-chlorobenzene, l-amino-3- glutaroylaminobenzene,l-amino-3- succinoylaminobenzene, l-amino-3- fumaroylaminobenzene,l-amino-2,5-

dimethoxybenzene, l-amino-2,S-diethoxybenzene,lamino-Z,S-diacetylaminobenzene, laminonaphthalene,Z-aminonaphthalene-7-sulphonic acid, l-aminobenzene, 2,5-dioxyaceticacid, l-amino- Z-methoxy-S-phenoxybenzene and N-3-amino-4-methylphenyl-urea.

The trisazo dyestuffs of formula l include dyestuffs of formula whereinR, denotes a hydrogen. or a chlorine atom, or an acetylamino group, Rdenotes a hydrogen or a chlorine atom or a methyl or propionylamine or aB-carboxypropionylamino group, R denotes a hydrogen atom, or a methoxyor ,B-hydroxyethoxy group, D, denotes a phenylene, naphthylene,toluylene, anisoylene, chlorophenylene, or triazolylene residue, E,denotes a phenylene residue and G, denotes a hydrogen atom or a methylgroup, the residues D, and E,-OG, being different from one another, theresidue OG, being bound to E, in 2- or 4-position with relation to theazo group, NH-CO being bound to D, in nonadjacent position with relationto the azo group and NHCO- being bound to E, in 3-position with relationto the azo group.

Preferred yellow dyestuffs for example correspond to the formula I) so H4 I l wherein R denotes a chlorine atom or a methyl group, (7)XCO--D-N=N-E--CO-X R denotes a methoxy or hydroxyethoxy group, R de- 6notes a hydrogen atom or a methoxy group, the residues of formulaewherein X denotes a halogen atom and D, E and G have the abovesignificance.

The residues D and D may for example be derived H) O CH from thefollowing diazo components: and n-l 3 2--n 3-aminobenzene-l-carboxylicacid,4-aminobenzene-lcarboxylic acid, 4-amino-3-methylbenzene-llcarboxylic acid, 3-amino-4-methylbenzenel 3 1 2 carboxylic acid,3-amino-4-methoxybenzenel carboxylic acid, 3-amino-4-chlorobenzenelbeing different from one another, and n denotes l or 2. 7 carboxylicacid. 5-amino-2-chlorobenzene-l- Amongst these dyestuffs. those offormula carboxylic acid, 4-amino-2-chlorobenzene-l- SO H 0-R )N=t NH -Cso 1 H3C 503B 3 n-l 2 n are particularly suitable, wherein R; denotes amethyl carboxylic acid, S-amino-l,2,4-triazole-3-carboxylic orhydroxyethoxy group and n denotes 1 or 2. 40 acid. 4-amino-l-naphthoicacid, 5-amino-l-naphthoic A particularly suitable dyestuff is of formulaacid and 5-amino-2-naphthoic acid.

The residues E and E may for example be derived 3 from the followingcoupling components:

1-hydroxybenzene-Z-carboxylic acid,

N=I\ NH" CO l-hydroxybenzene-3-carboxylic acid,

\ l-hydroxybenzene-4-carboxylic acid, l-hydroxy-4- l H Cmethylbenzene-Z-carboxylic acid, l-hydroxy-5-,

H 3 methylbenzene-Z-carboxylic acid, l-hydroxy-6- 3methylbenzene-Z-carboxylic acid, l-hydr0xy-4- chlorpbenzene-Z-carboxylicacid, l-hydroxy-S- methoxybenzene-Z-carboxylic acid and 5-chlorosalicylic acid.

3 0"CH3 The condensation may be effected according tov I known methodsand may be advantageously carried out @nhflk NHTCOWT in a polar solventfor example water or especially a H polar organic solvent for exampledimethylformamide,

l H 3 diethylacetamide or N-methylpyrrolidone. It is also ad- 3vantageous to carry out the condensation in the pres- O ence ofacid-binding reagents for example tertiary Th ll d t ff f f l (1 may allbe man, amines or alkali metal carbonates. The condensation facturedaccording to the same processes. An advantamay also be carried out inSolvents which themselves geous process is characterised in that acompound of act as acid'blnding agents for example Py or f lmethylpyrrolidone already mentioned.

A N=N B NH The aminoazo dyestuffs of formula (6) may be manu- 2 facturedaccording to known methods for example by wherein A and B have the abovesignificance, is concombining a diazo compound of an amine of formuladensed with dicarboxylic acid dihalides of formula A-NH wherein A hasthe significance mentioned, ad

vantageously in an acid medium, with a monoamine of formula H-BNHcapable of coupling, wherein B has the above significance.

The dicarboxylic acid dihalides of formula (7) may be manufactured bydiazotisation of an aminobenzene carboxylic or aminonaphthalenecarboxylic acid or of an amino triazole carboxylic acid or estersthereof, and coupling with a compound of formula H-E, wherein E has theabove-mentioned significance, if desired followed by alkylation of ahydroxyl group in the 0- or pposition in the residue E, and reaction ofthe azobenzene dicarboxylic acid thus obtained with a halogenatingagent, for example phosphorus pentachloride, phosphorus trichloride,thionyl chloride or phosgene, if desired in the presence of an inertsolvent with or without the addition of, for example, pyridine ordimethyl-,

formamide as catalyst.

Another process for the manufacture of trisazo dyestuffs of formula (1)is characterised in that a diazonium compound of an amine of formulawherein A and B have the significance mentioned above is coupled with acompound of formula (9) CO-Nl-l-Bh=N A wherein A, B and E have thesignificance mentioned above and G represents a hydrogen atom.

The diazonium compounds of the amines of formula (8) can be obtained invarious ways. Either a carboxylic acid halide'of formula wherein X hasthe significance already mentioned, is

condensed with a compound of formula (6), the nitro group reduced to theamino group and diazotised, or a carboxylic acid halide of formulawherein X has the significance already mentioned and Y represents theresidue NH-Z or -N=Z, wherein Z represents a removable protective group.is condensed with a compound of formula (6) the protective grou'p splitoff and the amino group diazotised. Suitable protective groups are forexample phthaloyl, carbalkoxy, carbophenyloxy, carbobenzoxy ortriphenylmethyl groups.

The compounds of formula (Il) may be advantageously manufactured byreacting the derivatives of the aminocarboxylic acids with thedicarboxylic acid anhydrides or the reactive halogen compounds of theprotective groups in an aqueousalkaline medium or in an inert solvent.if desired in the presence of compounds which add hydrogen halides forexample pyridine or triethylamine. After saponification and conversionto the carboxylic acid halide, preferably the chloride or bromide, thereaction with an aminoazo dyestuff of formula (6) is then carried out inthe usual manner. The manufacture of products having protective groupsand the splitting off of the protective groups under the ap' propriateconditions are known from protein chemistry.

As examples of compounds from which suitable carboxylic acids and theirderivatives may be derived. the compounds of the following formulae forexample may be mentioned:

coon coon COOH coon COOH N02 N02 N02 I CH3 I N02 (:1 N0

cooa

2 oca The trisazo dyestuffs of formula (I) can be used for variouspurposes, for example in the production of photographic materials andparticularly advantageously as image dyestuffs for the silver dyestuffbleaching process. Valuable photographic materials which contain atleast one layer having a dyestuff of formula (1) on a support canaccordingly be manufactured in the usual manner by known methods.

In particular, the trisazo dyestuffs may be present in a multi-layermaterial which on a layer support contains a layer which is dyed with agreenish-blue dyestuff and is selectively sensitive to red, over this amagentacoloured layer which is selectively sensitive to green andfinally a yellow-coloured layer which is selectively sensitive to blue.

The trisazo dyestuffs of formula (1) can be used in the various layers.

The dyestuffs of formulae (2), (3), (4) and (5) are particularlysuitable for the layer which is sensitive to blue in a silver dyestuffbleaching process.

The dyestuffs of formula (I) may also be incorporated into an auxiliarylayer or especially into a layer adjacent to the light-sensitive layer.

.The dyestuffs of formula (I) are very diffusionresistant in the usuallayers. They do not tend to change to an opalescent to cloudy form ingelatine layers on drying and storage. and they can be readily reducedin the bleaching bath to form harmless and/or easily washed-outdecomposition products.

The dyestuffs of formula l are distinguished by particularly high colourstrength and purity of shade. Grey shades which appear neutral to theeye over the entire density range can be produced with them, for exampleby combining a yellow dyestuff of formula (4) or (5) with one each of asuitable magneta and cyan dyestuff.

Compared to other trisazo dyestuffs, the dyestuffs of formula (1) arequite exceptionally distinguished by their good solubility andcompatibility with cations, es-

7 8 pecially calcium ions. They are nevertheless extraordioff and themixture is slowly allowed to cool to room narily diffusion-resistantover a pH range of -1 1. temperature. The yellow crystals which haveseparated In many cases it is particularly difficult to displace arefiltered and washed with 2.00 ml of N- the absorption of yellowdyestuffs by small amounts. methylpyrrolidone. The residue is boiledwith 50 ml of for example ynm towards ng r gh r to 5 methanol for onehour whilst stirring, filtered and flatten an excessively steep flank ofthe absorption washed three times with 2.50 ml of methanol each curve,particularly in the irection of long r wavetime. The residue is thenboiled for one hour with 40 lengths, as can under certain circumstancesbe desirel f h l d 6,00 l of potassium acetate able to Produc:e aneutral y h when PP P solution whilst stirring. filtered hot, rinsedfour times ately combining all three dyestuffs, over all density 10 i h4 l f h l h i d d i d at 60 ranges. C in vacuo. 4.75 g of the dyestuff Aof formula 3 OCH The present invention therefore also provides photoareobtained. graphic material, especially for the silver dyestuff bleachingprocess, which contains on a support, at least EXAMPLE 2 one layerhaving a dyestuff of one of formulae l to 2.1. p-Aminobenzoic acid ethylester is diazotised in (5). the usual manner and coupled withp-hydroxybenzoic Percentages given in the manufacturing examples acidmethyl ester. A yellow dyestuff of melting point which follow arepercentages by weight. 123 C is obtained. The hydroxyl group of thisdyestuff is methylated in the usual manner with dimethyl sulphate inacetone in the presence of potassium hydrox- EXAMPLE 1 ide. Themethylation product has a melting point of 153 C after recrystallisationfrom 100 acetic acid.

1.1.. 2-Aminonaphthalene-4.8-disu1phonic acid is The ester groups aresaponified with sodium hydroxide diazotised in the usual manner andcoupled with 2- and the saponification product is crystallised fromdimethoxy-S-methylaniline. methylformamide. The acid has a melting pointof 305 1.2. p-Aminobenzoic acid ethyl ester is diazotised in t 308 C,

the usual manner and coupled with salicylic acid 4 g of this acid aresuspended in 6.7 ml of toluene.

methyl ester. A yellow azo dyestuff is obtained which and after adding 3drops of dimethylformamide are melts at 151 C after recrystallisationfrom acetone. mix d with 4 g of thionyl chloride. The reaction mix- Thehydroxyl group of this dye-stuff is methylated in ture is then warmed to100 C whilst stirring. After 10 the usual manner with dimethyl sulphatein acetone in minutes all the material dissolves. The mixture is thepresence of potassium hydroxide- The resulting heated for a further 20minutes to 100 to 105 C. a furmethylation product melts at 140 C. 4-ther 6.7 ml of toluene are added and the mixture is al-Methoxyazobenzene-3.4'-dicarboxylic acid of melting lowed to coolslowly. The product is filtered, washed point 275 to 278 C is obtainedby saponification of with 20 ml of petroleum ether and crystallised from30 the two ester groups. m1 of benzene. 3 g of the acid chloride ofmelting point 400 g of this acid are dissolved in 400 ml of toluene 120C are obtained. and 63 ml of dimethylformamide at 80 C. miXed at 2.2.5.4 g of the yellow dyestuff manufactured acroom temperature with 245 mlof thionyl chloride. and cording to 1.1. are dissolved in 44 ml of N-the temperature is raised to C in 1 hour- The mi -methylpyrrolidone at120C. The solution is allowed to ture is stirred for a further two hoursat 90 C, filtered cool to 80 C a d 1.5 ml of pyridine and added. 2.5 ghot and the filtrate slowly allowed to cool to 0 C. The of the productaccording to 2.1. are then introduced mixture is filtered and theresidue washed three times with d ti i Th ddi i f h id hl id with 300 mlof petroleum ether each time. cording to 2.1. is continjed until nodyestuff 1.1. can be 430 g of yoellow needles of melting point 138 C aredetected chromatographically in the reaction mixture. obtained. Theclear reaction solution is mixed with 150 ml of ace- 1.3. 5.40 g of theproduct manufactured according to tone, filtered. and the residue washedwith 50 ml of ac- 1.1. are dissolved in 44 ml of N-methylpyrrolidone atetone. The residue is boiled with 50 m1 of methanol for 120 C. Themixture is then cooled to 80 C, 1.50 ml one hour whilst stirring,filtered hot and washed three of dry pyridine are added and 2.50 g ofthe product times with 20 ml of methanol each time. The residue ismanufactured according to 1.2. are introduced whilst boiled for one hourwith 40 m1 of methanol and 6 ml stirring. The addition of the productaccording to 1.2. of 20 alcoholic potassium a tat l ti fil d iscontinued until no further product according to 1.1. hot and washed dourtimes with 10 ml of methanol can be detected chromatographically in thereaction each ti mixture. The stirrer and the heating are then switched2.7 g of the yellow dyest ff B f f l so, 301 J 1 SO.l\ 3

\=N -NHCO- N=N I 3 so K 3 L on are 0btained- 15 are obtained.

EXAMPLE 3 EXAMPLE 4 3.1. 2-Methoxyaniline-5-carboxylic acid methyl esteris diazotised in the usual manner and coupled with salicylic acid methylester. The resulting dyestuff is methylated with dimethyl sulphate inknown manner in acetone in the presence of potassium hydroxide and thetwo carboxyl groups are then saponified.

3.3 g of the resulting dyestuff are suspended in 20 ml of benzene andmixed with 5 g of phosphorus pentachloride. The mixture is heated to 80C for one hour, allowed to cool to room temperature, and the resultingyellow crystals are filtered. washed with 3 ml of benzene and 20 ml ofpetroleum ether.

Yield 2.1 g; melting point: 165 C.

3.2. 8 g of the product manufactured according to 1.1. are dissolved in60 ml of N-methylpyrrolidone and 10 ml of pyridine at 120 C and thenmixed at 80 C with 4 g of the product manufactured according to 3.1. Theaddition of the product according to 3.1. is continued until no productmanufactured according to 1.1. can be detected chromatographically inthe reaction 4.1. 2-Aminonaphthalene-4.8-disulphonic acid is diazotisedin the usual manner and coupled with Z-B- hydroxyethoxy-S-methylaniline.

4.2. 5.5 g of the dyestuff manufactured according to 4.1. are dissolvedin 44 ml of N-methylpyrrolidone at 120 C, mixed with 1.5 ml of pyridine,and 2.5 g of the product according to 1.2. are introduced into thissolution at 80 C. The addition of product according to 1.2. is continueduntil no product according to 4.1. can be detected chromatographicallyin the reaction solution. The mixture is then allowed to cool slowly toroom temperature and the product is filtered, rinsed with 10 ml ofN-methylpyrrolidone and the residue boiled with 50 ml of alcohol for onehour whilst stirring. It is then filtered and the residue washed threetimes with 25 ml of alcohol each time. The residue is again boiled forone hour with ml of methanol with the addition of 6 ml of 20 7tpotassium acetate solution, filtered and washed three times with 10 mlof methanol each time.

4.6 g of the yellow dyestuff D of formula solution. The reactionsolution is then mixed with 300 are obtained.

ml of acetone. and the product is filtered and washed three times with50 ml of acetone each time. The residue is boiled with 100 ml ofmethanol and 10 ml of a 20% solution of potassium acetate in methylalcohol for oca ca oa 3. i con-11% CH3 I K EXAMPLE 5 5.l.2-Aminonaphthalene-4,8-disulphonic acid is diazotised in the usualmanner and coupled with 3-none hour, filtered and washed three timeswith 50 ml propionylaminoaniline.

of methanol each time.

6 g of the yellow dyestuffC of formula 5.2. 1.0 g of the dyestuffaccording to 5.1. is dissolved in 20 ml of N-methylpyrrolidone at roomtemperature 1 l 12 and 0.35 g of the product according to 1.2. areintro- 75 ml of petroleum ether and immediately further produced intothis solution. The addition of product accessed. cording to 1.2. iscontinued until no product according 7,3. 7 g of the dyestuffmanufactured according to to 5.1. can be detected chromatographically inthe re- 7,] ar dissolved in 70 ml of N-methylpyrrolidone and actionsolution. The dyestuff formed is precipitated by 7 ml of pyridine at 70C and the acid chloride obtained adding 200 ml of acetone, filtered, theresidue disfrom 7.2. is slowly added at this temperature, the prosolvedin 50 ml of water and the dyestuff precipitated gressive condensationbeing checked during the addiwith potassium acetate, filtered and washedthree times tion by the disappearance of the amino group which is with 5ml of methanol each time. recognisable by diazotisation and coupling ina spot 0.6 g of the yellow dyestuff E of formula test. When no furtheramino group can be detected, the

3 COCH CH I NI\ NH-CO-ON@ 0011 NH SOK 3 L) CO-NH N=1\ j S K C(.)CH Cl-II is obtained. reaction solution is stirred into 200 ml of acetone andEXAMPLE 6 the dyestuff which has separated is filtered and twice washedwith 100 ml of acetone each time. 6.1.2-Aminonaphthalene-4,8-disulphonic acid is The residue is boiled with 50ml of methanol and 5 diazotised in the usual manner and coupled with mlofa "/1 solution of potassium acetate in methyl al-5-chloro-2-methoxyaniline. cohol for 10 minutes. filtered and washedthree times 6.2. A procedure analogous to 5.2 is followed and 0.6 withml of methanol at 60 C. g of the yellow dyestuff F of formula 5 g ofdyestuff G of formula K0 8 OCH N=N- i NH-co-@ N-=i\ 0011 (jg L 3 Cl 803kg (11 co-1\ N= CH O (1.7) K0 5 is obtained.

OCl-l K035 3 C 3 co-ua --N=N $03K oca l (18) 3 are obtained.

' 7.1. 2-Aminonaphthalene-4,8-disulphonic acid is 8.1.2-Aminonaphthalene-4,8-disulphonic acid is diazotised in the usualmanner and coupled with 2- diazotised in the usual manner and coupledwith 3- methoxy-S-methylaniline. succinylaminoaniline.

7.2. p-Aminobenzoic acid is diazotised in the usual 3 g of finely P edyestuff HCCOrdiflg t0 8.1- manner and coupled with salicylic acid. aresuspended in ml of N-methylpyrrolidone and 5 44.8 g of the resultingdyestuff are suspended in 90 ml of Py and this suspension is mixed at Cml of benzene, and mixed with 58 ml of thionyl chlo- 60 with 2 g of4-meth0Xyaz0benzene-3,4-diearboxylie ride and 1 1.2 ml ofdimethylformamide. The mixture is acid dichloride (m nufacturedaccording to example heated to 55 to 60 C for one hour; a clear soluti i1.2.). Acid chloride is added until no further amino produced. This isallowed to cool and hydrochloric acid g p is detectable f r i z is i n npling in gas and sulphur dioxide are removed from the reaction a spottest. The reaction solution is stirred into 300 ml solution by pumpingthe reaction vessel to 16 mm Hg of acetone. and the dyestuff which hasseparated out is for one hour. The residue is stirred with a mixture of30 filtered and washed three times with 50 ml of acetone ml of benzeneand ml of petroleum ether, filtered, each time. The residue is suspendedin ml of methpressed, washed with a mixture of 25 ml of benzene andanol; 2.5 ml of a 20% solution of potassium acetate in methyl alcoholare then added, the mixture is boiled for minutes, the product isfiltered hot and washed three times with 50 ml of methanol each time at60 C.

1.6 g of the dyestuff H of formula I 3 coca ca 00011 are obtained.

EXAMPLE 9 9.1. Z-Methoxyaniline-S-sulphonic acid is diazotised 20 inknown manner and coupled with 2-methoxy-5- methylaniline.

9.2. 6 g of the dyestuff according to 9.1. in 60 ml ofN-methylpyrrolidone and 3 ml of pyridine are heated to 80 C and mixedwith 2 g of 4-methoxyazobenzene- 3,4-dicarboxylic acid dichloride(manufactured according to example 1.2.). Acid chloride is added untilno further amino group is detectable by diazotisation and coupling in aspot test.

The reaction solution is stirred into 300 ml of ace- 3 tone and thedyestuff is filtered and washed three times with ml of acetone eachtime.

uwco-Oam-Ckwmg diazotised in the usual manner and coupled withlaminonaphthalene.

SOK

I CO-CH CH COOH 10.2. 6 g of the dyestuff according to 10.1. aresuspended in 100 ml of methylpyrrolidone and 6 ml of pyridine, heated toC and mixed with 2 g of 4- methoxyazobenzene-3,4-dicarboxylic aciddichloride (manufactured according to example 1.2.). Acid chloride isadded until no further amino group is detectable by diazotisation andcoupling in a spot test. The reaction solution is stirred into 800 ml ofisopropanol and the product is filtered, washed with 300 ml ofisopropanol and twice with ml of alcohol.

The residue is suspended in 100 ml of methanol, mixed with 20 ml of a 207: solution of potassium acetate in methyl alcohol, the solution boiledfor 15 minutes. the product is filtered hot and washed with 100 ml ofmethyl alcohol.

4.8 g of the dyestuff J of formula are obtained.

EXAMPLE 11 11.1. 2-Amin0naphthalene-4,8-disulphonic acid is 50diazotised in the usual manner and coupled with 2methoxy-S-methylaniline.

0011 0011 iPneu-G- NH-CO-ON=NQ 0on CH3 3 on com N= so K 3 OCH 1 3 so Kare obtained.

l 1.2. p-Aminobenzoic acid ethal ester is diazotised in the usual mannerand coupled with hydroxynaphthalene-2-carboxylic acid methyl ester.

A yellow dyestuff of melting point 181 C is obtained. 11.3. 2.6 g of thedyestuff 1 1.2. are introduced into a mixture of 80 ml of acetone and2.8 g of powdered potassium hydroxide. the mixture is heated to 50 C for30 minutes. and 4.8 ml of dimethyl sulphate are then added during 15minutes. The mixture is boiled for 3 hours, poured on to 100 g of ice,mixed with 50 ml of 257( ammonia. filtered, and the residue washed withwater.

2.2 g of crude product are obtained and this is recrystallised from 600ml of alcohol and l g of charcoal. The resulting dyestuff has theformula (22) and melts at 138 C.

COOCH 11.4. 38 g of the dyestuff according to 11.3. are boiled for 10minutes in 200 ml of isopropanol with the addition of 30 ml of 10 Nsodium hydroxide solution. The reaction solution is mixed with 1.000 mlof water, rendered acid to Congo Red with hydrochloric acid.

cooled to C, filtered, and the residue washed with water. After dryingin vacuo at 100 C the reaction product is recrystallised fromdimethylformamide. Yield of compound of formula (27 21 g, melting point246C.

COOH

1 1.6 5 g of the dyestuff manufactured according to 1 1.1. in 50 ml ofmethylpyrrolidone and 5 ml of pyridine are heated to 80 C and mixed atthis temperature with 3 g of the acid chloride according to l 1.5. Theaddition of acid chloride is continued until no further amino group isdetectable by diazotisation and coupling in a spot test. The reactionsolution is then cooled to 20 C, stirred into 250 m1 of acetone,filtered and the residue washed with 200 ml of acetone. The residue istaken up in 100 ml of methyl alcohol, mixed with 25 ml ofa 20 7csolution of potassium acetate in methyl alco- COCl OCH

hol. boiled for 15 minutes. filtered hot and washed with 100 m1 ofmethyl alcohol.

5.2 g of the dyestuff K of formula OCH SO K

EXAMPLE 12 12. 1. 2-Amino-o-acetylaminonaphthalene-4,8- disulphonic acidis diazotised in the usual manner and coupled with3-succinylaminoaniline.

12.2. 3 g of finely powdered dyestuff according to 12.1. are suspendedin 60 m1 of N-methylpyrrolidone and 5 ml of pyridine and this suspensionis mixed at 80 C with 2 g of 4-methoxyazobenzene-3,4'-dicarboxylic aciddichloride. Acid chloride is added until no further amino group isdetectable by diazotisation and coupling in a spot test. The reactionsolution is stirred into 300 m1 of acetone, filtered and the productwashed three times with 50 ml of acetone each time. The residue issuspended in 100 ml of methanol, mixed with 2.5 m1 ofa 20% solution ofpotassium acetate in methyl alcohol, boiled for 15 minutes, filtered hotand washed three times with 50 m1 of methanol at 60 C each time.

are obtained.

4O 2 g of the dyestuff offormula 30 K UyNfll-O-Nll-CRCM Q NH 1 l I K I(26) co S 3 co I CH CH CH COOH S0 K =1\ 0on 3 NH CO-I\HO--N= I NH CHO-CH CH COOH are obtained.

EXAMPLE 13 13.1. 67 g of S-amino-l.2,4-triazole-3-carboxylic acid aresuspended in 300 ml of acetic acid/propionic acid 1:1. 200 ml of 37 7Ihydrochloric acid are added thereto, the mixture is cooled to C and 130ml of 4N sodium nitrite solution are added in several poritions.Diazotisation is carried out for one hour at 0 C.

The diazonium salt solution is poured into 80ml of salicylic acid methylester which have been diluted with 100 ml of methanol. The pH value israised from 3 to 9 by dropwise addition of 650 ml of 30% sodium hy-.

droxide solution. The mixture is stirred for 24 hours at 0 to C. Theintensely red-coloured suspension is heated to 50 C, filtered, and theresidue is recrystallised from 8,000 ml of water.

Yield 71 g 48.8 "/1 of a yellow powder which decomposes above 260 C andcorresponds to the formula (27) i 1-N I ll COOCl-l COOH 13.3. 3.8 g ofthe intermediate product of formula (28 in 50 ml of thionyl chloride and1 ml of dimethylformamide are stirred for 1 hour at 50 to 55 C.Thereafter the excess thionyl chloride is evaporated in vacuo at 50 C.The acid chloride is then further processed for the manufacture of therequired dyestuff.

13.4. 7 g of the coupling product from diazotised 2-aminonaphthalene-4,8-disulphonic acid and methoxy-S-methylaniline aredissolved in 150 m1 of N- methylpyrrolidone and directly added to theacid chlo-' ride of 13.3. After 12 hours stirring at room temperaturethe mixture is warmed to 60 C for 30 minutes and the dyestuff isprecipitated by adding 500 ml of acetone. The precipitated dyestuff isfiltered, the residue is dissolved in 30 ml of water. diluted with 300ml of methanol, and 5 ml of 7 N potassium acetate solution are added.The product is filtered and dried in vacuo at 50 C.

Yield 1.1 g of the orange dyestuff M of formula 18 EXAMPLE 14 14.1. 12.8g of the intermediate product of formula (27) (91 7t content) aresuspended in 100 ml of dimethylformamide; 35g of powdered potassiumcarbonate are then added. followed after half an hour by 19 mlofdimethyl sulphate 26 g). Foaming immediately starts with a slight risein temperature. Thereafter the mixture is heated to 60 70 C for 5minutes. and 100 ml of water and 2 N hydrochloric acid to give a pH of 7are added to destroy the excess dimethyl sulphate. The reaction mixtureif kept for 5 minutes at 70 C and concentrated until a thick crystalsludge is obtained which is filtered, washed with ml of methanol anddried in vacuo at 50 C.

Yield 4.5 g.

The product is purified by recrystallization from 50 ml of ethanol and3.5 g ofa yellow product of melting point 152 to 165 C of the formula nH CH DOC-C CN= OCH COOCH are obtained.

14.2 3.2 g of the intermediate product of formula (30) in 40 ml of 1 Nsodium hydroxide solution are heated to 90 C for 45 minutes. The mixtureis then neutralised with 2 N hydrochloric acid and the precipitate isfiltered. It is dried in vacuo at 50 C.

Yield 1.4 g of a yellow powder which decomposes (31) in 30 ml of thionylchloride and 1 ml of dimethylformamide are stirred for minutes at 50 to55 C.

The mixture is heated to reflux temperature for a short time and theexcess thionyl chloride is evaporated in vacuo. The resulting acidchloride is then further processed as follows.

14.4. 3.0 g of the coupling product from diazotised2-aminonaphthalene-4,8-disulphonic acid and 2- methoxy-S-methylanilineare dissolved 'in 50 ml of N- methylpyrrolidone and directly added tothe acid chloride of 14.3. After 12 hours stirring the mixture is heatedto 50 C, kept for 30 minutes at this temperature and then filtered, andthe filtrate is precipitated by adding 500 ml of acetone. The mixture isfiltered, the residue is dissolved in 30 ml of hot water and diluted OHN n NHCO C\\N c N NQ I 0011 $03K A oca com N= 03K I with 300 ml ofethanol, and ml of 7 N potassium acetate solution are added. The productis filtered and dried in vacuo at 50 C.

Yield 0.8 g of the yellow dyestuff N of the formula In accordance withExample 1 the dyestuffs O and P of the following formulae are prepared:Dyestuff O of the formula CH 503K 3 N= -c0- c1 0on N= (33) 803K 0on ca803K Dyestuff P of the formula CH 503K 3 fijj-wnb mi-co-Qw \OCH ca (34)803K 3 3 C 3 803K swim-6 w I OCH oca In accordance with Example 12 thedyestuffs Q, R and S of the following formulae are prepared:

s HN

' so K co H i 3 9 3* 13 N (35) 33 9 2 I II N= NHCOC\ N 10 OH N =N u 803K3 CH3 803K GOO-5% N= I 15 CH oca 9 I ocH 3 803K CH2 803K ca 0 CH2 3 200H OCH 3 so K 3 Dystuff R of the formula N= NH-COO-N (:1 \)CH3 CH3 (36)so 1 3 803K comm-pm CH3 I 0 01 Dyestuff S of the.formula CH 803K 3 =N\4% NH-COO-N 01 CH 3 i 2 7 0H =N ca -CO- N= 5on o 1 I CH2 803K 9Absorption maxima Dyestuff in nm EXAMPLE 15 The following layers aresuccessively applied to an 7 opaque white acetate film provided with anadhesive layer:

l. Silver bromide emulsion in gelatine, sensitive to red, containing thecyan dyestuff of formula 2. Colourless gelatine layer without silverhalide. 3. Silver bromide emulsion in gelatine, sensitive to green.containing the magenta dyestuff of formula )C l -NHCO-HN 50 N:

HZN 0.00

so H

80 R 4. Yellow filter layer containing the dyestuff of formula c1 0 OQE@4112 =N S H 3" 5. Silver bromide emulsion in gelatine, sensitive toblue. containing the yellow dyestuff A of formula 12).

The gelatine layers can also contain additives for example wettingagents, hardeners and stabilisers for the silver halide. In otherrespects the procedure followed is such that the individual layerscontain 0.5 g of the particular dyestuff and an amount of silver bromidecorresponding to 1 to 1.2 g of silver per square metre of film.

This film is exposed to red, green and blue copying light under acoloured diapositive. Thereafter the copy is developed in accordancewith the following instructions:

1. 6 Minutes development in a bath which in one litre of water containsg of anhydrous sodium sulphate, 0.2 g of l-phenyl-3-pyrazolidone, 6 g ofhydroquinone, 35 g of anhydrous sodium carbonate, 4 g of potassiumbromide and 0.3 g of benztriazole;

2. 5 minutes soaking;

3. 6 minutes fixing in a solution of 200 g of crystalline sodiumthiosulphate and 20 g of potassium metabisulphite in 1 litre of water;

4. 5 minutes soaking;

5. 3 to l2 minutes colour bleaching with a solution which in one litreof water contains 50 to 80 g of potassium bromide, 40 to 80 g ofthiourea, 35 to 80 g of 30% sulphuric acid and if desired 0.01 g of2-amino-3- oxyphenazine;

6. 10 minutes soaking;

7. 5 minutes bleaching of residual silver with a solution of g ofcrystalline copper sulphate. g of potassium bromide and 15 ml of 30%hydrochloric acid per litre of water;

8. 5 minutes soaking;

9. 5 minutes fixing as specified under 3;

l0. 5 minutes soaking.

The resulting positive image for viewing in reflected light is fast toslight and of the permanence required for documents.

Instead of dyestuff A, dyestuffs B to S can also be used with equallygood results.

We claim:

1. Photographic material for the silver dyestuff bleaching process thatcontains on a support at least one silver halide emulsion layer and inat least one layer a trisazo dyestuff of the formula wherein each Adenotes a benzene or naphthalene resi-' due which is unsubstituted orsubstituted by a halogen 23 24 atom or an alkyl, alkoxy, nitro oracetylamino group B-carboxypropionylamino group, R denotes a hydroandcontains 1 to 3 sulphonic acid groups, each B degen atom or a methoxy orB-hydroxyethoxy group D notes a benzene residue which is unsubstitutedor subdenotes a phenylene. naphthylene, toluylene, anisoystituted by atmost 2 halogen atoms, or alkyl, alkoxy, lene, chlorophenylene ortriazolylene residue, E, de-

hydroxyalkoxy, alkoxyalkoxy, acylamino, carbox- 5 notes a phenylene.residue and G, denotes a hydrogen yacylamino, carboxyalkyl, carboxy orphenoxy groups atom or a methyl group, the residues D, and E -OG,

or denotes a naphthalene residue, and wherein D debeing different fromone another, -OG being notes a benzene or naphthalene residue or atriazole bound to E in 2- or 4-position with relation to the azoresidue, E denotes a benzene residue and G denotes a group, NHCO beingbound to D, in nonhydrogen atom or an alkyl group containing 1 to 5 carladjacent position with relation to the azo group and l bon atoms, D andE each are unsubstituted or substi- -NHCO being bound to E in 3-positionwith relatuted by a halogen atom or an alkyl, alkoxy or phenyl tion tothe azo group. 4 group, the residues D and E O-G being different 3.Photographic material according to claim 1 that from one another beingbound t0 E in 0f contains on a support at least one layer containing aposition with relation to the azo group, AN= trisazo dyestuff of theformula NBNHCO being bound to D in non-adjacent wherein R denotes achlorine atom or a methyl group, position with relation to the azo groupand R denotes a methoxy or hydroxyethoxy group, R debeing bound to E i3- notes a hydrogen atom or a methoxy group, the resiposition withrelation to the azo group. dues of formulae 2. Photographic materialaccording to claim 1 that contains on a support at least one layercontaining a trisazo dyestuff of the formula SO H being different fromone another, and n denotes 1 or 2. wherein R denotes a hydrogen or achlorine atom, or 4. Photographic material according to claim 1 that anacetylamino group. R denotes a hydrogen orachlocontains on a support atleast one layer Containing a rine atom or a methyl or propionylaminogroup or a iriSflZO y ff 0f the rmu a =1 -NH-C H c S0311 3 H N SO3H (H)-0-CH N: NH n-l 3 2-n where R; denotes a methyl or hydroxyethoxy groupand n denotes I or 2.

S. Photographic material according to claim 1 that contains on a supportthe trisazo dyestuff of the formula so H 3 -N=t\ NH-C0 H c 3 s0 N $0 11O-CH3 WQNHO 1 11- c 3 O-CH so H 3

1. PHOTOGRAPHIC MATERIAL FOR THE SILVER DYESTUFF BLEACHING PROCESS THATCONTAINS ON A SUPPORT AT LEAST ONE SILVER HALIDE EMULSION LAYER AND INAT LEAST ONE LAYER A TRISAZO DYESTUFF OF THE FORMULA
 2. PhotographicmateriaL according to claim 1 that contains on a support at least onelayer containing a trisazo dyestuff of the formula
 3. Photographicmaterial according to claim 1 that contains on a support at least onelayer containing a trisazo dyestuff of the formula
 4. Photographicmaterial according to claim 1 that contains on a support at least onelayer containing a trisazo dyestuff of the formula
 5. Photographicmaterial according to claim 1 that contains on a support the trisazodyestuff of the formula